Nunes Dos Santos Comprido Laura, Klein Johannes E M N, Knizia Gerald, Kästner Johannes, Hashmi A Stephen K
Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Department of Chemistry, University of Minnesota, 207 Pleasant St SE, Minneapolis, MN, 55455, USA.
Chemistry. 2017 Aug 10;23(45):10901-10905. doi: 10.1002/chem.201702023. Epub 2017 Jul 19.
The potential of vinyl Au species to react either through a controlled π- or σ-pathway is demonstrated. This nomenclature is directly derived from the orbitals of the vinyl Au species leading to the newly formed bonds. When the π-bond of the vinyl Au intermediate is transformed into a σ-bond, we name it π-pathway, and a σ- to σ- transformation is named σ-pathway. Examples of reactions following these pathways are a Au-catalysed [3,3]-sigmatropic rearrangement and a protodeauration reaction. These reactions have been studied using intrinsic bond orbitals (IBOs) and allow for the clear identification of these pathways. Energies for the reaction path of the Au-catalysed [3,3]-sigmatropic rearrangement were in addition computed using CCSD(T)-F12. Analysis of the intrinsic reaction coordinate (IRC) of the [3,3]-sigmatropic rearrangement using IBOs further allows us to refine the previous mechanistic proposal and identifies a hidden intermediate along the reaction path.
已证明乙烯基金属金物种通过可控的π-或σ-途径发生反应的可能性。这种命名直接源自乙烯基金属金物种形成新键所涉及的轨道。当乙烯基金属金中间体的π键转变为σ键时，我们将其命名为π-途径，而σ-到σ-的转变则命名为σ-途径。遵循这些途径的反应示例包括金催化的[3,3]-σ迁移重排反应和质子脱金反应。已使用内禀键轨道（IBO）对这些反应进行了研究，从而能够清晰地识别这些途径。此外，还使用CCSD(T)-F12计算了金催化的[3,3]-σ迁移重排反应路径的能量。使用IBO对[3,3]-σ迁移重排反应的内禀反应坐标（IRC）进行分析，进一步使我们能够完善先前的机理推测，并确定反应路径上的一个隐藏中间体。
